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TMACH-1,2-HOPO, a versatile tripodal metal chelator: complexation, solution thermodynamics, spectroscopic and DFT studies

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Abstract

A new tripodal siderophore-mimic hexadentate chelator, N,N’,N’’-(((1R,3R)-cyclohexane-1,3,5-triyl)tris(methylene))tris(1-hydroxy-6-oxo-1,6-dihydropyridine-2 carboxamide), (TMACH-1,2-HOPO) containing three 1,2-hydroxypyridinone units attached to a cyclohexane ring through amide linkage at 1,3 and 5 positions have been designed, synthesized, and characterized by FT-IR, 1H NMR, 13C NMR, ESI-MS, and electronic spectroscopy. The solution thermodynamics and photophysical properties of the ligand and its metal complexes (M = La3+, Gd3+, and Lu3+) were investigated experimentally and theoretically in an aqueous medium. The pKa values for the ligand were found to be 8.32, 6.86, and 5.45. In an aqueous solution, the ligand formed complexes of the type MLH3, MLH2, MLH, and Mion. Additionally, it formed three hydrolyzed species, MLH− 1, MLH− 2, and MLH− 3 at a higher pH. DFT studies were performed, which support the experimental results. The nature of bonding between the lanthanide ions and the ligand was explained by NBO, Morokuma Ziegler energy decomposition analysis (ETS-NOCV).

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Funding

One of the author (Dibyajit Dash) is grateful to the management of Sant Longowal Institute of Engineering and Technology, Longowal, for financial support.

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  1. Department of Chemistry, Sant Longowal Institute of Engineering and Technology, Longowal, 148106, Punjab, India

    Dibyajit Dash & B. K. Kanungo

  2. Department of Chemistry, National Institute of Technology, Kurukshetra, 136119, Haryana, India

    Shalini Singh & Minati Baral

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Dibyajit Dash: Experimental work, manuscript preparation, Shalini Singh: Verification and validation of Data, Minati Baral and B K Kanungo: Concept, Supervision and Editing.

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Details of experimental section, HRMS data, IR, 1H NMR, 13C NMR, spectrophotometric titration curves of ligand with lanthanide ions and the energy level diagrams of LH3 and its deprotonated species are given in Figure S1, Figure S2, Figure S3, Figure S4, Figure S5 and Figure S6 respectively. The calculated and experimentally obtained chemical shifts, stretching frequencies are presented in Table S1, whereas the DFT simulated thermodynamic parameters, bond energy, HOMO and LUMO energy of neutral and deprotonated ligand species are available in Table S2 of the Supporting information.

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Dash, D., Singh, S., Baral, M. et al. TMACH-1,2-HOPO, a versatile tripodal metal chelator: complexation, solution thermodynamics, spectroscopic and DFT studies. J Incl Phenom Macrocycl Chem 104, 109–127 (2024). https://doi.org/10.1007/s10847-024-01221-9

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